Tsukano Chihiro, Yamamoto Sho, Takemoto Yoshiji
Graduate School of Pharmaceutical Sciences, Kyoto University.
Chem Pharm Bull (Tokyo). 2015;63(9):710-9. doi: 10.1248/cpb.c15-00417.
The synthesis of α-acyloxyketones via the migration of a propargylic ester followed by the intramolecular nucleophilic addition of the resulting allene was achieved using a cationic platinum catalyst. The optimized conditions for this transformation were determined to be 3 mol% of Pt(cod)Cl2, 3 mol% of AgNTf2, and 3 eq of water in toluene at 100 °C, and these conditions were successfully applied to the synthesis of a wide variety of α-aryl-α-acyloxyketones. The mechanism of this reaction was evaluated in detail based on the results of isotope labeling experiments using H2(18)O.
通过炔丙基酯迁移，随后使生成的丙二烯进行分子内亲核加成反应来合成α-酰氧基酮，这一过程是使用阳离子铂催化剂实现的。该转化反应的优化条件确定为：在100℃下，于甲苯中使用3 mol%的Pt(cod)Cl2、3 mol%的AgNTf2和3当量的水，并且这些条件已成功应用于多种α-芳基-α-酰氧基酮的合成。基于使用H2(18)O进行的同位素标记实验结果，对该反应的机理进行了详细评估。
